Combination process of effluent refrigeration and closed cycle refrigeration



D. H. PUTNI-:Y 2,906,796 COMBINATION PROCESS 0F EFFLUENT REFRIGERATION sept. 29, 1959 AND CLOSED CYCLE REFRIGERATION 2 Sheets-Sheet 1 Filled May 23, 1956 mt @NG PB 229i 2,906,796 COMBINATION PROCESS OF EFFLUENT REFRIGERATION D. H. PUTNEY Sept. 29, 1959 AND CLOSED CYCLE REFRIGERATION 2 Sheets-Sheet 2 Filed May 23, 1956 ,as applied in alkylation c 2,906,796 Patented Sept. 29, 1959 Kansas City, Kans., assgnor to Strat- Kansas City, Mo., a

This invention relates to efiluent refrigeration and refers more particularly to a method of achieving the benefits of effluent refrigeration fo-r at least one first chemical reaction system not employing effluent refrigeration in the reaction step which is communicable with at least one second, like chemical reaction system which does employ effiuent refrigeration in its reaction st ep, said method also benetitting the effluent refrigeration process in said chemical reaction system.

Effluent refrigeration shall mean any system yof refrigeration used in a reaction system which employs as a refrigerating medium any part or all of the effluent issuing from a reactor or settler for cooling the reactlon zone, wherein the reactor and settler are maintained at a pressure sufficient to prevent vaporization therein and the pressure on the efuent is subsequently reduced in the refrigeration cycle, and whereinrvapors evolved from the effluent in the refrigeration cycle are condensed and returned as part of the feed tothe reactor.

The invention is viewed as applicable to any chemical reaction system wherein the reactants are contacted in a reaction step, one of the reactants is in excess and capable of being evaporated with pressure reduction'and wherein it is desirable to cool the reaction step.

As a specific example, the invention will be presented systems wherein isoblltane and olefins are contacted with liquid acid catalyst (such as and including hydroiluoric and sulfuric acid) and a mixture of hydrocarbons is withdrawn with acid catalyst as efiiuent from the reaction step, but chemical reaction systems employing other reactants, otherv catalysts or no catalysts, etc., which have the above listed characteristics are contemplated as being able to benefit by and be included within the invention. Some otherchemical reaction systems to which the instant invention isv applicable in either general or limited form include the production of ethyl benzene for styrene manufacture by condensationA of benzene with ethylene or ethyl chlorideusing a catalyst such as aluminum chlorideV and beniene as excess reactant material, hydrocarbon reaction' systems in which alum-inum bromide might be used asa catalyst (aluminum bromide being quite soluble in hydrocarbons) and reaction systems employing boron trifluoride as a catalyst (the latter being a gas and corrosive). ln one of its limited forms, the invention would `also be ajgiplicable` to any chemical reaction employing effluent refrigeration in which a harmful or deleterious material is found in the eiuent reaction mixture (volatile, sticking, corrosive, ete).

Therefore, an object of the present invention is to provide a method of gaining at least some ofthe benefits of effluent refrigeration for a first chemical'reaction system wherein the reactants are contacted in a reaction step, one of the reactants is in excess and capable of being evaporated with pressure reduction and it is desirable to cool the reaction step, said first system not employing effluent refrigeration, but which' is within communicating distance of a second chemical reaction system of like character employing eflluent refrigeration. y

Another object of 'the present invention 1s fi proud@ such a method which rn y improve the benefits ofefiiiient refrigeration in the second chemical reaction system.

i Another objectl of the invention is to obtain indirect heat exchange of they input of reactants to both such chemical reaction systems rather thantrrierely the single reaction system already employing effluent refrigeration.

Another object of the invention is to increase the recycle Vof unreactedV reactant in the first chemical reaction system, as is alreadyl the case in the eliliient refrigeration system. Y, 1 l

y Another object of rthe invention is to provide an integrated efiiuent refrigeration system which atleast in part embraces boththe original and second chemical reaction systems wherein the heat exchanging of the reactant feeds and `the recycle unrea'cted reactant feeds can be regulated between the two systems as desired. l ,I

Another object of the' invention is to provider-such an integratedl efiiuent refrigeration system which embraces at least in part both reaction systems whereby the required capacity of the refrigeration system employed in the original reaction system may be reduced if vdesired whiie maintaining the same" or lower react-ion temperature.

Another object of the invention is to pro-vide a greater circulation of liquid phase effluent reaction mixture through the reactor cooling elements ofthe seco-nd chemical reaction system when only such liquid phase efiiuent refrigeration is employed. 'l

Another object of the, invention is` toprovide a greater quantity of liquid eind vapor phase reaction mixture volume through the reactor cooling elements` of the4 adjacent systems reaction step when suchtotal'circulation is employed. t

Anotlif bjects of the invention is toprovidea greater quantity of liquid eduction into the reactor cooling elements of the adjacent reaction step when such eduction is employed in the system. o l

Another object of the invention is to provide means permitting recycle of excess unreacted reactant to both lreaction steps even in systems employing objectionable catalytic materials' or' impurities which are carried over into the unreacted excess reactant. y j Y Another object of the invention is to reduce the deisobutanizer load on the original reaction step where the chemicalreactions are the alkylation of isobutanes with olefins with acid catalyst.

Another object of the present invention is to operate two alkylation units in combination, oneV vvith'clost'ed cycle refrigeration and theother withefiluent refrigeration Vso that for a` given totalv amount of isobutane a lower vacid consumption Aand a higher quality product will be realized than when each of the units is operated separately without benefit of the combination. l l

Other and further objects of the invention will appear in the course'of *the following description thereof:

In the drawings, which form a part of the instant specification and are to vberead in conjunction therewith, there are shown two embodiments of the invention,

Fig. l is a schematic iiovv diagram of one embodiment of the invention, said embodiment being particularly adapted to chemical reaction systems wherein isobutane and olefins are contacted with liquid sulfuric acid in an alkylation system.

Fig. Zis a schematic lio-w diagram of a second embodiment of the invention wherein isobutane andV olefins Szllfurc acid-system (Fig. 1)

Referring to the drawings, and more particularly to Fig. l, at is shown theV shell of a reactor or contacting vessel equipped with anopen ended circulating tube 11. :"At one end of the circulating tube is an impeller 12 which serves the purpose of a circulating pump 1n cooperation with the circulating tube. Within the circulating "tube 11 are a plurality of heat exchange elements 13 comprising a tube bundle provided with a distributing head 14 enclosing one end of the reactor. The impeller 12 is mounted on a shaft 15 rotated through a reduction l gear 16 by any suitable source of power or prime mover such as an electric motor or steam turbine diagrammatically shown at 17.

Circulation of heat exchanging uid such as ammonia or propane through the tube bundle or heat exchange elements is accomplished by any conventional heat exchange unit such as the conventional closed cycle refrigeration unit illustrated. In this unit, fluid from the condensate accumulator 18 is fed through flow line 19 by pump 20 (optional) and line 21 into the distributing head 14 through the tube bundle 13 and out of the distributing head 14 through flow line 22 to a compressor 23 then through How line 24 to a condensation step diagrammatically shown at 25 and through flow line 26 into the condensate accumulator 18. Such closed cycle refrigeration units are well known in the art and any conventional variation thereon may be employed.

Circulation within the reactor is established by the impeller 12 through the annular space between the shell 10 and the circulating tube 11 around the cooling or heat exchanging tubes 13 and back to the impeller.

' Alkylation of the isoparainic hydrocarbons by the olenic hydrocarbons takes place in the reactor While the mixture is being rapidly circulated and agitated by irnpeller 12 which assures mixing of the hydrocarbons and acid catalyst.

Referring now to the lower right-hand side of Fig. 1, a second reactor similar in its construction to that of the first reactor just described, is shown schematically. This reactor, in commercial practice, must be positioned so as distributing head 31 enclosing one end of the reactor.

The impeller 29 is mounted on a shaft 32 rotated through a reduction gear 33 by any suitable source of power or prime mover such as an electric motor or steam turbine diagrammatically shown at 34.

The ow of uid through the tube bundle 30 or heat exchange elements will be later described. Circulation within the reactor is established by the impeller 29 through the annular space between the shell 27 and circulating tube 28 around the cooling or heat exchange tubes 30 and back to the impeller. Alkylation of the soparanic hydrocarbons by the olefinic hydrocarbons takes place in the reactor while the mixture is being rapidly circulated and agitated by impeller 29 which assures mixing of the hydrocarbons and acid catalyst.

It is contemplated in the case of each of the reactors 10 and 27 shown, that the two separate chemical reactions may be carried out at least partially in vessels without heat exchange tubes. exchange operations relative each tion to reduce the temperature of the exothermic reaction would be accomplished in a later stage, but, in both instances illustrated, the apparatus shown, with built-in In such case the heat` separate chemical reacheat exchange elements in the reactor itself, is preferred.

Referring back to the rst reactor in the center of Fig. l, to simplify an understanding of the-process relative said rst reactor, it will be described in conjunction with the apparatus. Olefnic hydrocarbons and isobutane are introduced to the system through lines 35 and 36, respectively, and are combined in feed pipe 37 prior to passage through heat exchanger 38. Recycled isobutane returned through pipe 39 is introduced into the hydrocarbon mixture on the downstream side of heat exchanger 38, constituting the feed by introduction into pipe 4). Fresh acid is fed to the rst reactor through line 41 and recycle acid from settler 42 is combined with the fresh acid through pipe 43 or diverted from the system through pipe 44.

The hydrocarbons supplied through lines 35 and 36 are mixed with recycled isobutane added through line 39 and then mixed in the first reactor with the acid catalyst introduced through lines 41, 43 and 45. As previously mentioned, alkylation of the isoparaffinic hydrocarbons by the olenic hydrocarbons takes place in the reactor while the mixture is being rapidly circulated and agitated by impeller 12 which assures a thorough and intimate dispersion of the hydrocarbon and acid catalyst.

The efuent mixture of hydrocarbons and acid is discharged from the reactor through pipe 46, passing to the acid settler 42 Where it is permitted to separate into a hydrocarbon phase and an acid phase. The acid phase is Withdrawn from the bottom of the settler and directed to the reactor through pipes 43 and 45 while a portion of the acid separated in the settler may be diverted through the spent acid discharge line 44 to maintain a proper acidity and proportioning of reactants and catalyst in the system.

If the chemical reaction which is conducted in the rst reactor is such that the catalyst need not or cannot readily be separated from the reactants or is one employing no catalyst, the separation step may be omitted. An example of such a process would be the alkylation of isobutane with ethylene using an aluminum bromide catalyst which is soluble in the hydrocarbons.

The hydrocarbon phase separated in the settler 42 is discharged from the top through pipe 47 and this hydrocarbon phase material is run to the vicinity of the second reactor 27 and entered into the effluent hydrocarbon phase material in said second reactor system in a manner to be described after the reaction system of the second reactor 27 is set forth. Both the reactor 10 and settler 42 are operated at pressure sufficiently high to prevent vaporization therein. This pressure is maintained by bacl; pressure regulating valves 67 or 81 as hereinafter described.

Referring now to the second reactor system shown in the lower right hand corner of Fig. 1, olenic hydrocarbons and isobutane in excess are introduced to the system through lines 48 and 49, respectively, and are combined in feed pipe 50 prior to passage through heat exchanger 51. Recycled isobutane from fractionation is returned through pipe 52 and introduced into the hydrocarbon mixture on the downstream side of heat exchanger 51, constituting a portion of the feed supplied to the second reactor 27 through pipe 53.

Fresh acid is supplied to the system through line 54, being combined with recycle acid from settler 55. The acid phase from settler 55 is returned to the reactor 27 through lines 57 and 58. The fresh acid and recycle acid enter the second reactor through pipe 59.

Hydrocarbons supplied through lines 48 and 49 combined with recycled isobutane are mixed in the reactor with the acid catalyst introduced through pipe 59. As previously mentioned, alkylation of the isoparatiinic hydrocarbons by the olefnic hydrocarbons takes place in the reactor while the mixture is being rapidly circulated and agitated by impeller 29 which assures mixing of the hydrocarbons and acid catalyst.

The eiuent mixture of hydrocarbons and acid is discharged from the second reactor through pipe 60, passing if? ih? Cid Sill' 55 where it is permitted to separate .into a hydrocarbon phase ,and an acid phase. If thereiisobutane with ethylene as set forth above relative the rst reactor, using an aluminum bromide catalyst which is soluble .in the hydrocarbons. The acid phase is withdrawn from the bottom ofthe settler and directed to the reactor through pipes 57 and 58 vwhile a portion of the acid separated in the settler maybe diverted through the .spent -acid discharge line 61 to maintain a proper acidity .and proportioning of reactants andcatalystin thevsystem.

Both the reactor 27 and settler 55 are operated at pressure suiiiciently high to prevent -vaporization therein. This pressure is maintained by back pressure regulating valves 67 or 81 as hereinafter described.

The hydrocarbon phase separated in the settler 55 is discharged from the top through pipe 62 and joined by the hydrocarbon phase material from the first reactor through pipe 47. The combined hydrocarbon phase ma- -terial may then be directed either through line 63 or line 64 by manipulation of the valves 65 and 66 in these lines. I-f directed through line v64, pressure is reduced at pres- 'sure'reduction valve 67 resulting in vaporization of a portion of the isobutane component and chilling of the material, after which at least a portion and preferably mosty of all the liquid-vapor mixture, at greatly increased velocity, is directed through lines 68 and 69 to the distributing head 4431 -of the reactor. This distributing head is divided by a partition 31a which causes the coolant introduced through lines 68 and 69 to pass throughthe heat exchange elements 30, thence into theopposite side of the distributing head and out through the pipe 70. Back pressure valve 67 is designed to hold sufcientback pressure on the reactor-settler system to prevent appreciable evaporation of the hydrocarbon components contained therein. If desired, a portion of the'reduced pressure hydrocarbon phase material may be passed directly to the'flash drum 71by line 72. Valves 73 and 74 regulate the relative amounts of this flow.

For example, when alkylating isobutane with butylenes in a system wherein a small amount of propane is also present, the reaction temperature will Vnormally be controlled at 33 F. to 55 F. and the back pressure maintained on the settler by valve 67 will be in the order of 40 p.s.i.g. to 100 p.s.i.g. VUpon passing pressure reduction valve 67, pressure upon the 'hydrocarbon efuent is reduced to the order of 0 p.s.i.g. to l0 p.s.i.g., causing a considerable portion of the lighter components of the yeffluent to vaporize resulting inthe cooling of the `entire 4hydrocarbon effluent mixture. Dependinguponthe pressure established within the cooling elements or tube bundle of the reactor, the temperature o f the hydrocarbon ethuent phase will be reduced to a ligure normally within the range of 15 F. to 30 F. by evaporative cooling, making it suitable for use as the cooling medium for the reactor.

Upon leaving the cooling elements 30' of thereactor, the chilled and partially vapcrized effluent passes from vthe lopposite `side of the distributing head 31 through 'line 70 to eflluent flash drum 71 Where the vapor and liquid portions of the effluent are separated. A liquid vlevel control 75,rnanipulating valve 76 regulates the discharge of liquid from the eiuent flash drum 71 through pipe77. A second draw-off pipe 78, controlled by valve 79 connects into pippe r69 atan eductor 80. The Afunc- .tion of the eductor is to utilize the energy of the high velocity stream of uid passing through line 68 after pressure reduction at valve 67. This stream of hydrocarbons owing at high Velocity draws into pipe 69 liquidfrom the liash drum 71 through pipe 78.

Hydrocarbon phase may be directed through line 63 from the acid settler, pressure reduced at valve-S1 and `the material chilled by ,evaporativecooling .in vflash drum vdischarged through line 62 and combined with the rst reactor hydrocarbon phase, that is, the combination flow, may be split and a portion passed through line 64 and the remainder through line 63. Valves 66 land 65 control the relative amounts of these flows if such is the case.

Liquid Withdrawn from the eluent ash drum through pipe l77 is returned by pump 82 and .pipes 83 and .84 to heat exchangers 38 and 51 Where it is .brought `inlheat exchanging relationship ywith the incoming vvfeed stocks supplied through pipes 37 and 50, respectively. 'From .the heat exchangers 38 and 51, the liquid passes thence through lines to S6 to the neutralization and fractionating steps diagrammatically shown at 87.

The `vapors separated from the hydrocarbon eiuent in the flash drum or suction trap 71 pass off from the top through line 88 to compressor 89 from .which they ,are discharged through line 90 to condenser 100. A portion of the condensate from condenser is diverted through lines 101 and 102 to isobu-tane ash drum 103 operated at the same pressure as flash dru-m 71v since both pressures are controlled Aby the suction pressureon compressor 89 and have an open communicating line 1614. interposed in line 101 is a pressure reducing valve 165 which holds suicient back pressure on the condenser 10@ to make possible substantially total condensation of Vthe hydrocarbons at the temperature which can be main through line 107, pressure reducing valve 108 and pipes 182 to the isobutane flash drum. Back lpressure valve 188 in line 107 functions in the same mannervas yreducing valve previously described. It will be understood, of course, that if less build-up o-f propane is desired in the reactor system, all of the condensate from condenser 100 may be passed to the depropanizer through line v106 and returned to the system after depropanization through line 167. In such case none of the condensate woul pass through pressure reducing valve 105.

Liquid hydrocarbons withdrawn from suction trap or ash drum 71 through pipe 77 are pumped, as previously explained, through pipes 83 and 85, .84 and86 to fraction- -atio-n and there separated into streams of propane, isobutane, normal butane, light alkylate` and alkylate bottoms. In some operations utilizing efuent refrigeration, the alkylate bottoms are eliminated, or alkylate of about 380 F.E.P. (Fahrenheit end point) entirely suitable for motor fuel is obtained without any fractionation of the alkylate. When the lalkylate is fractionated to recover a fraction of lower end point suitable for `use rin aviation gasoline of current specifications, the bottoms fraction is suitable for motor fuel. The product streams are normally removed from the system through pipes 109, "110, 111 and 112. The isobutane stream taken overhead from the deisobutanizer tower is recycled either through'lines 36 and 49 or through pipe 113, pressure reduction valve 114 and pipe 1012 to the isobutane ilash drum from which it is returned to the reaction stage through pipe `115, pump 116 and pipes 39 and 52 to the -rst and second reactors, respectively. Fresh isobutane feed Vto thetwo systems may also be brought in either through lines 36 7 and 49 or through pipe 117 which connects through line 102 with the isobutane ash drum 103. All of the streams entering this isobutane flash drum 103 are subjected to :w reduced pressure established by the suction of the compressor and are thereby self-refrigerated.

The vapors evolved in the isobutane flash drum by this evaporative cooling are passed through line 104 to the compressor 89 while the chilled liquid from the drum, principally isobutane, is returned to the two reactors as described.

In actual practice, it has been found that when the pressure on the hydrocarbon phase both withdrawn from the settler 55 and added through line 47 is reduced and the material thereafter separated in an evaporative cooler (passed through line 63 directly to the ash drum), any pump (not shown) used to recycle the liquid as a coolant to the second reactor must be of considerable capacity in order to provide sufiicient velocity through the cooling elements to effect a high rate of heat transfer. To drive such a pump necessitates considerable horsepower, which is expensive. Again, when none of the liquid from the flash drum 71 is passed through the heat exchanger in the reactor and only the combined hydrocarbon effluent from line 64 is used, there is a relatively large volume of vapor and a limited amount of liquid passing through the cooling elements. Under these conditions it is sometimes difiicult to keep the internal surface of the cooling elements covered with liquid, which greatly reduces the effectiveness or cooling effect of the coolant. As stated previously, it has been found that both of these objections can be eliminated by causing circulation through the cooling elements of both the combined hydrocarbon effluents of the two reactors separated in the settlers 42 and 55 after pressure reduction at valve 67, together with additional liquid withdrawn from the suction trap through line 7S. By operating with both liquid and vapor passing over the cooling tubes 30 of the second reactor 27 without prior separation, less turbuf lence and less carryover from the flash drum 71 is experienced. By operation it would seem likely and would normally be predicted that there would be a build-up of pressure which would force the liquid and vapor from the pressure reducing valve 67 up into the suction trap, especially if there were a low level or the liquid seal were broken. However, with the eductor 80 placed as explained, it actually works as desired with both liquid and vapor first passing to the cooling coils 30 of the second reactor 27, thence to the suction trap 71, even if the charge pump S2 to the debutanizer or deisobutanizer should take off too much liquid from the suction trap 71 so as to break the liquid seal.

Regardless of the means used for effecting ow of coolant through the cooling elements of the reactor, the pressure of the hydrocarbon fluid leaving the acid settlers 42 and 55 must be reduced from settler pressure to suction trap or flash drum 71 pressure at some point. When this pressure is released, a considerable portion of the lighter components of the hydrocarbon effluent, primarily isobutane, is vaporized and a chilling effect takes place which reduces the temperature of the hydrocarbons to about 15 F. to 30 F. Considerable energy is expended across the valve 67 in which this pressure reduction takes place, and although the velocity in the line upstream of the valve may be in the order of two feet to ten feet per second, the velocity downstream after vaporizing an appreciable portion of the hydrocarbons usually exceeds one hnudred feet per second. The energy in this high velocity stream flowing through pipes 68 and 69 can well be utilized to increase circulation through the heat exchange elements in the reactor by introducing the stream into the liquid recycle line 78 from the flash drum 71 in such a manner that the high velocity stream will produce an inductive effect on the liquid from the suction trap or ash drum 71. This is accomplished as described either by extending line 68 carrying the high Nvelocity stream into an elbow in the liquid circulatingv line 78 as shown, or it can be accomplished by installing a conventional type eductor 80 in the liquid line from the flash drum 71 and introducing the chilled effluent from line 68 into the high pressure connection of the eductor so it serves as the energizing medium therein.

Although the invention has been described as applying to alkylation in which sulfuric acid is used as a catalyst, it is applicable as well to alkylation using hydrofluoric acid as the catalytic agent. Another process for which the invention is applicable is the production of ethyl benzene for styrene manufacture by condensation of benzene with ethylene or ethyl chloride using a catalyst such as aluminum chloride and benzene as excess reactant material.

Hydrofluorc acid system (Fig. 2)

Referring now to Fig. 2, and the primary reactor in the center of the figure, at 200 is shown the shell of the primary reactor equipped with an open ended circulation tube 201. At one end of the circulation tube is an impeller 202 which serves the purpose of a circulating pump in co-operation with the circulation tube. Within the circulation tube 201 are a plurality of heat exchange elements 203 comprising a tube bundle provided with a distributing head 204 enclosing one end of the reactor. The impeller 202 is mounted on a shaft 205 rotated through a reduction gear 206 by any suitable source of power or prime mover such as an electric motor or steam turbine diagrammatically shown at 207. Circulation within the reactor is established by the impeller within the annular space between the shell 200 and circulation tube 201 around the cooling or heating exchange tubes 203 and back to the impeller. Olenic hydrocarbons and isobutane in excess are introduced to the system through lines 208 and 209, respectively, and are combined in feed pipe 210 prior to passage through heat exchanger 211. Recycled isobutane from fractionation is returned through pipe 212 and introduced into the hydrocarbon mixture before reaching the heat exchanger 211, constituting a portion of the feed supplied to the reactor through pipe 213.

Fresh acid is supplied to the system through line 214, being combined with recycle acid from accumulator 215 and recycle acid from primary acid settler 216. The regenerated recycle acid is returned through line 217, pump 218 and line 219 while the recycle acid from primary acid settler 216 is returned to the reactor through line 220. The fresh acid, regenreated acid, and recycle acid enter the reactor through pipe 221.

Hydrocarbons supplied through lines 208 and 209 combined with recycled isobutane are mixed in the reactor with the acid catalyst introduced through pipe 221. Alkylation of the isoparaiiinic hydrocarbons by the olcnic hydrocarbons takes place in the reactor while the mixture is being rapidly circulated and agitated by impeller 202 which assures mixing of the hydrocarbons and acid catalyst.

Cooling medium is directed through line 222 to the distributing head 204 of the reactor. This distributing head is divided by a partition 204-a which causes the coolant introduced through line 222 to pass through the heat exchange elements 203, thence into the opposite side of the distributing head and out through the pipe 223. Any conventional cooling system such as a closed cycle cooling system employing Freon, propane or ammonia such as is shown in Fig. 1 may be employed. Cooling water lines may be employed to run water through the heat exchange elements as the heat exchanging medium.

The effluent mixture of hydrocarbons and acid is discharged from the reactor through pipe 224, passing first to the primary acid settler 216 where it is permitted to separate into a hydrocarbon phase and an acid phase. The acid phase is withdrawn from the bottom and is either returned to the reactor through pipes 220 and 221 or diverted through pipes 225 and 226 to the acid regenerator 227. Valves are interposed in these lines to gov- 9 ern 'the amount of acid returned to the reactor and diverted to the regenerator. *The hydrocarbon phase separated in primary settler V216 is discharged from the top through pipe 228 into 10 returned to the reactor through pipes 272 and 273v or diverted through pipes 275 and 276 to the acid regenerator 277. Valves are interposed in these lines to govern the amount of acid returned to the reactor 242 and diverted final acid settler 229. In the iinal settler, the eiiiuent 5 to the regenerator 277. l rnixture of hydrocarbons is permittedto separate from The hydloearbon Phase sepafaied in Primary settler whatever acid remains, approximately one percent by 258 iS diSCharged fiOIn 'die iop through Pipe 273 into Weight remaining in the hydrocarbon phase material, the final acid settler 279. In the final settler, the eliiuent'mixacid'bottoms 'being Withdrawn through a discharge line ture of hydrocarbons is permitted to separate from What- I 230 connected intorthe acid discharge pipe 225 through 10 ever acid remains, approximatelyy one percent by 'weight :whichl the acidv bottoms from settlers216 and 229 pass remaining in the hydrocarbon phase material, the acid through linesf225- and 226 to acid regenerator 227 4which bottoms being Withdrawn il'nougll a discharge line 230 is, equippedvvithheating coil 231. A preheater 232 is inconnected into the acid discharge pipe275 through which terposed in pipe 226 ahead of the regenerator. lInput and the acid bottoms from the primary acid settler flow to discharge fluid lines 233 and 23,4 serve to circulate a heatthe acid regenerator 277. The acid bottoms from settlers ing-medium through coil. 231 in the bodem of. the acid 26S and 279 pass through lines 275 and 276 to acidr reregenerator 227. Regenerated acid passes from the top 'generator 277 Which iS equipped-With heating coil 281. ffheregenerater 227 through line 235, and after. con- A preheater 282 is interposed in pipe 276 ahead'of the densationat 236 is delivered through pipe 237 into acid regenerator. Input and discharge iiuid lines 283 and 284 1 accumulator215. ABy-pass flow` line 238, controlled by 20 serve to circulate a heating medium through coil 281 in ,Va1ve1239,A may be used, to by-pass theregerlerator 227 the bottom of the acid regenerator 277. Regenerated acid oridivert a portion of the acid bottoms from the settlers passes'from the top of regenerator 277 through line 285,

. 5.216 '.and. 22-9 to accumulator 215. As 4previously sugand after condens-ation at 286 is delivered through pipe gested, acid from the accumulator 215 is returned through 287 into acid accumulator 267. By-pass flow line 28S,

' Alines-217 and v219 to the reactor. Sludge and tars are. 25 controlled by valve 289 may be used to by-pass rthe rev removed from the bottom of the regenerator 227 through generator 277 or divert a portion of the acid bottoms from 1in'e240 vmsuitable disposal. the settlers 268 and 279 to accumulator 267. Asvprevi- '1' lThefhydrocarbon.phase separated in the final acid setously Suggested, seid from the accumulator 267 isrei tler .229 vis discharged from. the top throughpipe 241 and turned through lines 269 and 271 to the reactor. Sludge .direeted to the hydrocarbonv phase discharge line on the 30 and tars are removed from the bottom of the regenerator '-second settler ofthe second reactor. This second reactor through line 290 to suitable disposal.

;.lsystemlwill new be described and the employment of the The hydrocarbon phase separated in the final acidsethydrocarbon phase material from the first reactor system tiel' 279 iS diSCllarged fr0-In the top through pipe'291 .smeren/ith, joined by the hydrocarbon phase from top of the second i '.Rfeppingnowto the lowgpfighphand Side @f .Fig 2I 35 Sellier 229 Of the lI'St I'CaClOI 200 bIOllgl'llI thereflvom f 1242 is, shown the shell of areaetorequipped with an through pipe 241 and the combined streams may be 'open erided circulating tube 243, At one end of the cir. directed either through lines 292 or 293 by manipulation Cu1atingtube is an impeller 244 which serves the purpose of the valves 294 and 295 in these lines. If-'directed l.of.a.'circulating pump in cooperation with a circulating through line 293, pressure is reduced at pressure reduction jtube.' Withinthe circulating tube 243 are a plurality of 40 Valve 296 resulting invaporization of a portion ofithe -heat exchange elements 245 comprising a tube bundle isobutane component and chilling of the material, after .provided with. a distributing head 246 enclosing one end Which ei least a Portion and Preferably Inosi 01 all of the .-xofthe reactor. The impeller 244 is mounted on .a shaft liquid-Vapor mixture at greatly increased velocity is' di- .2471 rotated through a reduction gear 248 by any suitable rected through line 297 to the distributing head 246 of the isourceof power or prime mover such as an electric. motor reactor. This distributing head is divided by a partition ei-' Sani turbine diagrammatic-,ally Shown at 249, 24661 which causes the coolant introduced through line '.Oleiuichydrocarbons and isobutane in excess are intro- 297 t0 paSS through the heat exchange elements 245, ducedto the system through lines 250 and A251, respec- .thence into the oppo-site side of the distributing head and l z-tvely,.. and arecombined in feed pipe252`prior to passage out through the pipe '298. Back pressure -valve 296 is 'xthroughheat exchanger 253. Recycled isobutaue from 50 Adesigned to hold sufficient back pressure on the reactorfractionation is returned through pipe 254 and introduced settler SYStem to prevent appreciable evaporation of the into thehydrocarbon mixture before reaching theheat vhydrocarbon components contained therein. If desired, LeXChangerfZSS, constituting a portion of the feed supplied a portion ofthe reduced pressure hydrocarbon phase mate- .to thereactorv through pipe 255. rial from valve 296 may be passed directly to the lia-sh Freshfacid is supplied to the system through-1ine'266, 55 drum 299 by line 390. Valves 301 and 302 in lines 297 .,beingcornbined Withregenerated acid from accumulator and 300 regulate the relative amounts of this How.

:-267.Land recycle acid fromy primary acid-settler 268. .The Ina System wherein a small amount of propane is presregenerated aeidisreturned from the aeeurnulator 267 ent and the reaction temperature is controlled at about .through line 1269, pump 270 and line 271 while the recycle 33 F- to 55 F., the back pressure maintained onthe acid'from primary settler 268 is returned to the reactor 60 settler 279' by valve 296 will be in the order of 40 p.s.i.g. ,through line 272. The fresh acid, regenerated acid. and to `100 Psi-g- Upon passing pressure reduction Valve 296 recycleacidenter the reactorthrough pipe `273. Pressure upon the hydfoeebons Passing into 'ille Cooling Hydrocarbons supplied through lines 250 and 251 cemelements 245 is reduced to the order of 0 p.s.i.g. to 10 'bined` with. recycled isobutane are, mixed kin the reactor p.s.i.g., causing a considerable portion of the lighter coma with .the .acid :catalyst introduced through pipe 7273, 65 ponents of the etiiuent to vaporize, resulting in the cooling .'Alkylation of the isoparafnnio hydrocarbons bythe oleof the entire combined hydrocarbon phases from the Anicnhydrocarboris takesplace in the reactorwhilethe feaeiols 200 and 242 Depending upon 'die Pressure ,'mixtureiis being yrapidly circulated and agitated by 'imestablished Within the cooling elements of the tube bundle .1peller-'244whichassures mixingof'the hydrocarbons and 245 of the reactor 242, the temperature of the hydroacidcatalyst. Y carbon eiiluent phase will be reduced to a ligure normally e yThe eiiiuent mixture of hydrocarbons and acid is Vdis- Within the fange of'l5 F- to 30 F- by evaporative C001- charged from the reactor through pipe 274, passing first ing, making it suitable fol' use as the Cooling medium for to the primary yacidsettler 26S where it is permitted to the reactor 242. separate Ainto a hydrocarbon phase and an -acid phase. Upon leaving the cooling elements 245 ofthe reactor {Iheacidphase is Withdrawn from thebottom and is either @242, vthe chilled .and partially vaporized eiuent passes from the opposite side of the distributing head 246 through line 298 to effluent flash drum 299 where the vapor and liquid portions of the eflluent are separated. A liquid level control 303 manipulating valve 304 regulates the discharge of liquid from the eluent flash drum 299 through pipe 305. A second draw-off pipe 306 controlled by valve 307 connects into pipe 297 at an eductor 308. The function of the eductor is to utilize the energy of the high velocity stream of fluid passing through line 297 after pressure reduction at valve 296. This stream of hydro- -carbons flowing at high velocity draws into pipe 297 liquid from the flash drum 299 through pipe 306.

The combined hydrocarbon phase material from rcactors 200 and 242 may as well be directed through line 292 from the final acid settler 279, pressure reduced at valve 309 and the material chilled by evaporative cooling a flash drum 299. In such a situation, only the liquid i. portion of the hydrocarbon phase is returned as the cooling medium to the reactor 242 from the flash drum 299. Circulation of liquid through the cooling tubes in such case is effected by the gas lift effect of the vapors evolved within the tubes. It is contemplated as well that the hydrocarbon phase discharged from settler 279 through line 291 and combined with the hydrocarbons in line 241 from the first reactor system, that is, the totality, may be split and a portion of the combination passed through line 293 and the remainder through line 292. Valves 29S and 294 control the relative amounts of these flows in such an instance.

The liquid withdrawn from the effluent flash drum 299 through pipe 305 is returned by pump 310 and pipes 311 and 312 to heat exchangers 211 and 253 where it is brought in heat exchanging relationship with the incoming feed stocks in the two separate reactor systems supplied through pipes 210 and 252, respectively. From the heat exchangers 211 and 253, the liquid passes through lines 313 and 314 to neutralization and fractionation schematically shown at 315.

The vapors separated from the hydrocarbon eflluent in the flash drum 299 pass off through line 316 to condenser 317 from which the condensate may be split between two lines 318 and 319 regulated through valves 320 and 321, line 319 leading to eflluent flash accumulator 322 and line 318 leading to neutralization and fractionation steps to be later described. The effluent flash drum 299 is operated at a pressure in the order of 15 to 25 p.s.i.a. when the reactor is held at 50 F. The vapors leaving the flash drum 299 pass to the condenser 317 and to some extent at least, to accumulator 322 which are operated at approximately the same pressure. Condensate in accumulator 322 is recycled to the two reactor feed pipes 255 and 213 through pipes 323, pump 324 and pipes 325 and 326. Valves 327 and 328 regulate the amounts of these flows.

Cooling medium at the condenser 317 is provided by a closed cycle refrigeration system such as, for example, one utilizing Freon 12 or propane. This refrigeration system includes condenser coil 329 in condenser 317, the latter connected to compressor 330 by line 331, a line 332 leading from the compressor 330 to condenser 333 and pipe 334 connecting the condenser to receiver 335. A pipe 336 completes the closed cycle connecting receiver 335 with condenser 317. The condensing surface 329 is kept flooded with liquid refrigerant by level control 337 operating valve 338 which admits liquid refrigerant to condenser 317 from receiver 335. This refrigeration system is operated to provide a condensing temperature in the order of 15 F. It will be noted that the refrigeration system is operated as a closed cycle so that none of the refrigerant comes in contact with the hydrocarbons being processed or the hydrogen fluoride catalyst. Even more important, none of the hydrogen fluoride cornes in contact with the compressor 330.

By means of this refrigeration system, eflluent vapors are withdrawn from flash drum 299, condensed, and

their temperature is reduced commensurate with the temperatures of the circulating refrigerant. Under normal operating conditions, condensate leaving the condenser 317 will have a temperature of approximately 15 to 25 F. The quantity of isobutane in this condensate will normally be in the order of 4 to 7 parts by volume for each part of olefin in the fresh feed to reactor 242. The overhead from hte deisobutanizer (not shown except schematically in the fractionation 315) can thus be reduced by this same amount for any given condition of fixed quality and rerun yield of alkylate, or it follows if the deisobutanizer remains fixed, the concentration of isobutane in the reactor is considerably increased by the condensed vapors from this source, resulting in increased quality and yield of alkylate.

The desirability of recycling liquid from the flash drum 299 through the eductor 308 into the cooling coils of the second reactor system is the same as that described relative Fig. 1 and will not be repeated here.

A portion of the condensate from condenser 317 comprising the condensed vapors separated from the hydrocarbon effluent in the flash drum may be passed through line 318 relative the neutralization and fractionation steps 315 regulated by valve 320.

When propane is a component of any of the feed streams, a portion of the condensate from condenser 317 withdrawn through line 318 is diverted through pipe 339 to the depropanizer of the fractionation section diagrammatically shown at 315. This is necessary in order to purge the system of the same amount of propane as is contained in the feed stock, and after depropanization, this stream is returned to the system through line 340. It will be understood that if less build-up of propane is desired in the reactor system, all of the condensate from condenser 317 taken off through line 318 may be passed to the depropanizer through line 339 and returned to the system after depropanization through line 340.

Liquid hydrocarbons withdrawn from flash drum 299 through pipe 305 are pumped as previously described through pipes 311 and 312, heat exchangers 211 and 253 and pipes 313 and 314 to fractionation 315 and there separated into streams of propane, isobutane, normal butane, light alkylate and alkylate bottoms. In some operations utilizing effluent refrigeration, the alkylate bottoms are eliminated, or alkylate of about 380 F.E.P. (Fahrenheit end point) entirely suitable for motor fuel is obtained without any fractionation of the alkylate. When the alkylate is fractionated to recover a fraction of lower end point suitable for the use in aviation gasoline of current specifications, the bottoms fraction is suitable for motor fuel. The products streams are normally removed from the system through pipes 341, 342, 343 and 344. The isobutane stream taken overhead from the deisobutanizer tower in line 345 is recycled to the reactors through lines 212 and 254 having valves 351 and 352 thereon, respectively, pipes 212 and 254 leading from the valves to the feed lines 210 and 252.

Although the invention has been described in connection with hydrofluoric acid alkylation with reactor temperatures in the order of 50 F., it should be understood that the reactor may be operated at more elevated temperatures since in many cases alkylation units are operated with reactor temperatures of 60-70 F. or even as high as F. In such cases, the eflluent flash drum can be operated at higher temperatures and pressures and still provide satisfactory temperature difference between the refrigerating medium and chilled eflluent. For the transfer of heat in such cases, the closed cycle refrigeration system can also be operated at higher pressures and still provide satisfactory cooling medium for the flash vapor condenser.

Thus, it is seen that a method has been provided for gaining at least some of the benefits of effluent refrigeration for a first chemical reaction system not employing y `refiluentrefrigeration of communicating Y system 'rofllik character whichisgeniploying eflltuent refrigeration of its reaction step.

The method as shown in both specific examples may improve the benefits in the second chemical reaction system thus, for example, where only liquid phase effluent reaction mixture is circulated through the heat exchange elements of the second chemical reaction system, a greater circulation of such liquid phase material may be achieved in said second chemical reaction system due to the greater amount of liquid phase material in the fiash drum or suction trap. Again, in the modification of the method wherein the combined hydrocarbon phase efliuent mixtures are both circulated in totality after pressure reduction through the heat exchanging elements of the second reactor, a greater volume of such circulation is possible due to the combination ofthe eluent hydrocarbon phases from both reactors and thus a more efficient heat exchanging process in the second reactor is possible. Also, where liquid is educted from the fish drum or suction trap into the flow line into the second reactor heat exchanging elements, greater eduction and thus more efiicient heat exchange is possible due both to the greater quantity of liquid available in the flash drum and the greater volume of vapor and liquid being circulated through the heat exchanging elements.

The inventive method also has made possible as effluent refrigeration benefits to the first reactor, which does not employ in itself effluent refrigeration, first, indirect heat exchange of the input of reactants to the first reactor or first chemical reaction system, second, an increase in the recycle of unreacted reactant in the first chemical reaction system as is already the case in the second reactor or existing effluent refrigeration system, this latter benefit serving to reduce the deisobutanizer load on the original reaction step where the chemical reactions are the alkylation of isobutanes with olefins with acid catalyst, and, third, permitting the reduction of the required capacity of the original refrigeration system employed in the original reaction system if desired while maintaining the same or lower reaction temperature.

Additionally, the total system benefits from the combination in that an integrated efiiuent refrigeration system is provided which at least in part embraces both the original and second chemical reaction systems wherein the heat exchanging of the reactant feeds and the recycle of unreacted reactant feeds can be regulated between the two systems as desired as conditions vary relative thereto, these features permitting a much more flexible total system than either system by itself. Finally, the invention has been made applicable even in systems which employ objectionable catalytic materials or impurities which are carried over into the unreacted excess reactant whereby recycle of said excess unreacted reactant to both reaction steps is made possible.

Additionally, by operating two alkylation units in combination, one with closed cycle refrigeration and the other with effluent refrigeration, it is possible for a given total amount of isobutane to realize a lower acid consumption and make a higher quality product than when operating each unit separately without the benefit of the combination.

Thus it will be seen that the invention is well adapted to attain all the ends and objects hereinbefore set forth, together with other advantages which are obvious and which are inherent to the process.

It will be understood that certain features and subcombinations are of utility and may be employed without reference to other features and subcombinations. This is contemplated by and is Within the scope of the claims.

As many possible embodiments may be made of the invention without departing from the scope thereof, it is to be understood that all matter hereinabove set forth or as'illustrative and not in a limiting sense.

lsystem involving the alkylation of ,an alkylatable hydrovfcarboriwherein the reactants arecontacted inliqiiidiflhase in a reaction step, one of the reactants is in excess, relatively volatile, and capable of being evaporated with pressure reduction, and wherein it is desirable to cool said reaction system and a mixture is withdrawn as efiiuent from said reaction step, said first chemical reaction system being refrigerated by means other than effluent refrigeration to cool the reaction step, comprising the steps of reacting said first chemical reaction system and a. second like chemical reaction system employing effluent refrigeration to cool its reaction step in separate reaction steps, discharging effluent reaction mixtures from said first and second chemical reaction steps, reducing the pressure on said eiuent mixtures to vaporize excess reactant in said efiluent mixtures, passing at least the major portion of the combined reduced pressure efiiuent mixtures in indirect heat exchange with the second reaction mixture in its reaction step, passing said heat exchanged effluent mixtures to a separating step, separating said reduced pressure reaction mixtures into liquid and vapor components, and bringing at least a portion of the liquid component separated from said reduced pressure reaction mixtures into indirect heat exchange with the feed of reactants to both said first and second reaction steps.

2. A method of achieving at least some of the benefits of effluent refrigeration for a first chemical reaction system involving the alkylation of an alkylatable hydrocarbon wherein the reactants are contacted in liquid phase in a reaction step, one of the reactants is in excess, relatively volatile, and capable of being evaporated with pressure reduction, and wherein it is desirable to cool said reaction step and a mixture is withdrawn as effluent from said reaction step, said first chemical reaction system being refrigerated by means other than effluent refrigeration to cool the reaction step comprising the steps of reacting said first chemical reaction system and a second like chemical reaction system employing eiiiuent refrigeration to cool its reaction step in separate reaction steps, discharging effluent reaction mixtures from said first and second chemical reaction steps, reducing pressure on said effluent mixtures to vaporize excess reactant in said effluent mixtures, passing at least the major portions of the combined reduced pressure effluent mixtures in indirect heat exchange with the second reaction mixture in its reaction step, passing said heat exchanged efuent mixtures to a separating step, separating said reduced pressure reaction mixtures into liquid and vapor components, the vapor component separated from said reduced pressure reaction mixtures being condensed and recycled as part of the feed to both of said first and second reaction steps.

3. A method as in claim 2 wherein after the vapor component separated from said reduced pressure reaction mixtures is condensed, a portion is reevaporated from the condensed body of liquid to reduce the temperature thereof prior to recycling as part of the feed to both said first and second reaction steps.

4. A method as in claim 2 wherein at least a portion of the liquid component separated from said reduced pressure reaction mixtures returned to cool the second reaction mixture is brought into indirect heat exchange with the feed of reactants to said first and second reaction steps.

5. A method as in claim 1 wherein all of said reduced pressure reaction mixtures are passed in heat exchanging relationship with the reaction step in said second chemical reaction system.

6. A method as in claim 2 wherein all of said re- 15 16 duced pressure reaction mixtures are passed in heat 2,238,802 Altshuler etal. Apr. 15,1941 exchanging relationship with the reaction step in said 2,418,146 Upham Apr. 1, 1947 secondI chemical reaction system. 2,471,211 Hadden May 24, 1949 f Y 2,664,452 Putney Dec. 20, 1953 References Cited in the le of this patent 5 UNITED STATES PATENTS 2,123,021 Phillips July 5, 1938 

